This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. The types of dynamics-correlated experiments that we intend to pursue will utilize state-of-the-art experimental methodologies and instrumentation to study molecular transient spectroscopy on fast, sub-nanosecond time scales. Optical pump-probe, optical-pump/infrared-probe and dynamics Stokes shift experiments will be correlated with experiments such as transient optical pump-probe experiments. This work will delineate structure-function relationships engineered to bind donor - spacer - acceptor (D-Sp-A) supermolecules and covalently linked multi-cofactor assemblies. While these systems possess reduced structural complexity, they enable independent modulation of the local electrostatic forces that surround D and A. We will examine photoinduced PCET reactions in such systems using optical pump / optical probe and visible pump / IR probe spectroscopic methods, and correlate the observed dynamics with specific responses with specific structures.